If bodies are prepared with separately microscopically stationary states, and are then put into purely thermal connection with each other, by conductive or radiative pathways, they will be in thermal equilibrium with each other just when the connection is followed by no change in either body. But if initially they are not in a relation of thermal equilibrium, heat will flow from the hotter to the colder, by whatever pathway, conductive or radiative, is available, and this flow will continue until thermal equilibrium is reached and then they will have the same temperature.
One form of thermal equilibrium is radiative exchange equilibrium. [7] [8] Two bodies, each with its own uniform temperature, in solely radiative connection, no matter how far apart, or what partially obstructive, reflective, or refractive, obstacles lie in their path of radiative exchange, not moving relative to one another, will exchange thermal radiation, in net the hotter transferring energy to the cooler, and will exchange equal and opposite amounts just when they are at the same temperature. In this situation, Kirchhoff's law of equality of radiative emissivity and absorptivity and the Helmholtz reciprocity principle are in play.
Change of internal state of an isolated system
If an initially isolated physical system, without internal walls that establish adiabatically isolated subsystems, is left long enough, it will usually reach a state of thermal equilibrium in itself, in which its temperature will be uniform throughout, but not necessarily a state of thermodynamic equilibrium, if there is some structural barrier that can prevent some possible processes in the system from reaching equilibrium; glass is an example. Classical thermodynamics in general considers idealized systems that have reached internal equilibrium, and idealized transfers of matter and energy between them.
An isolated physical system may be inhomogeneous, or may be composed of several subsystems separated from each other by walls. If an initially inhomogeneous physical system, without internal walls, is isolated by a thermodynamic operation, it will in general over time change its internal state. Or if it is composed of several subsystems separated from each other by walls, it may change its state after a thermodynamic operation that changes its walls. Such changes may include change of temperature or spatial distribution of temperature, by changing the state of constituent materials. A rod of iron, initially prepared to be hot at one end and cold at the other, when isolated, will change so that its temperature becomes uniform all along its length; during the process, the rod is not in thermal equilibrium until its temperature is uniform. In a system prepared as a block of ice floating in a bath of hot water, and then isolated, the ice can melt; during the melting, the system is not in thermal equilibrium; but eventually, its temperature will become uniform; the block of ice will not re-form. A system prepared as a mixture of petrol vapour and air can be ignited by a spark and produce carbon dioxide and water; if this happens in an isolated system, it will increase the temperature of the system, and during the increase, the system is not in thermal equilibrium; but eventually, the system will settle to a uniform temperature.
Such changes in isolated systems are irreversible in the sense that while such a change will occur spontaneously whenever the system is prepared in the same way, the reverse change will practically never occur spontaneously within the isolated system; this is a large part of the content of the second law of thermodynamics. Truly perfectly isolated systems do not occur in nature, and always are artificially prepared.
In a gravitational field
One may consider a system contained in a very tall adiabatically isolating vessel with rigid walls initially containing a thermally heterogeneous distribution of material, left for a long time under the influence of a steady gravitational field, along its tall dimension, due to an outside body such as the earth. It will settle to a state of uniform temperature throughout, though not of uniform pressure or density, and perhaps containing several phases. It is then in internal thermal equilibrium and even in thermodynamic equilibrium. This means that all local parts of the system are in mutual radiative exchange equilibrium. This means that the temperature of the system is spatially uniform. [8] This is so in all cases, including those of non-uniform external force fields. For an externally imposed gravitational field, this may be proved in macroscopic thermodynamic terms, by the calculus of variations, using the method of Langrangian multipliers. [9] [10] [11] [12] [13] [14] Considerations of kinetic theory or statistical mechanics also support this statement. [15] [16] [17] [18] [19] [20] [21]
Distinctions between thermal and thermodynamic equilibria
There is an important distinction between thermal and thermodynamic equilibrium. According to Münster (1970), in states of thermodynamic equilibrium, the state variables of a system do not change at a measurable rate. Moreover, "The proviso 'at a measurable rate' implies that we can consider an equilibrium only with respect to specified processes and defined experimental conditions." Also, a state of thermodynamic equilibrium can be described by fewer macroscopic variables than any other state of a given body of matter. A single isolated body can start in a state which is not one of thermodynamic equilibrium, and can change till thermodynamic equilibrium is reached. Thermal equilibrium is a relation between two bodies or closed systems, in which transfers are allowed only of energy and take place through a partition permeable to heat, and in which the transfers have proceeded till the states of the bodies cease to change. [22]
An explicit distinction between 'thermal equilibrium' and 'thermodynamic equilibrium' is made by C.J. Adkins. He allows that two systems might be allowed to exchange heat but be constrained from exchanging work; they will naturally exchange heat till they have equal temperatures, and reach thermal equilibrium, but in general, will not be in thermodynamic equilibrium. They can reach thermodynamic equilibrium when they are allowed also to exchange work. [23]
Another explicit distinction between 'thermal equilibrium' and 'thermodynamic equilibrium' is made by B. C. Eu. He considers two systems in thermal contact, one a thermometer, the other a system in which several irreversible processes are occurring. He considers the case in which, over the time scale of interest, it happens that both the thermometer reading and the irreversible processes are steady. Then there is thermal equilibrium without thermodynamic equilibrium. Eu proposes consequently that the zeroth law of thermodynamics can be considered to apply even when thermodynamic equilibrium is not present; also he proposes that if changes are occurring so fast that a steady temperature cannot be defined, then "it is no longer possible to describe the process by means of a thermodynamic formalism. In other words, thermodynamics has no meaning for such a process." [24]
Entropy is a scientific concept that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the microscopic description of nature in statistical physics, and to the principles of information theory. It has found far-ranging applications in chemistry and physics, in biological systems and their relation to life, in cosmology, economics, sociology, weather science, climate change, and information systems including the transmission of information in telecommunication.
Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of thermodynamics which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology.
The second law of thermodynamics is a physical law based on universal empirical observation concerning heat and energy interconversions. A simple statement of the law is that heat always flows spontaneously from hotter to colder regions of matter. Another statement is: "Not all heat can be converted into work in a cyclic process."
The first law of thermodynamics is a formulation of the law of conservation of energy in the context of thermodynamic processes. The law distinguishes two principal forms of energy transfer, heat and thermodynamic work, that modify a thermodynamic system containing a constant amount of matter. The law also defines the internal energy of a system, an extensive property for taking account of the balance of heat and work in the system. Energy cannot be created or destroyed, but it can be transformed from one form to another. In an isolated system the sum of all forms of energy is constant.
The zeroth law of thermodynamics is one of the four principal laws of thermodynamics. It provides an independent definition of temperature without reference to entropy, which is defined in the second law. The law was established by Ralph H. Fowler in the 1930s, long after the first, second, and third laws had been widely recognized.
Thermodynamic equilibrium is an axiomatic concept of thermodynamics. It is an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable walls. In thermodynamic equilibrium, there are no net macroscopic flows of matter nor of energy within a system or between systems. In a system that is in its own state of internal thermodynamic equilibrium, no macroscopic change occurs.
A thermodynamic system is a body of matter and/or radiation separate from its surroundings that can be studied using the laws of thermodynamics. A thermodynamic system may be an isolated system, a closed system, or an open system. An isolated system does not exchange matter or energy with its surroundings. A closed system may exchange heat, experience forces, and exert forces, but does not exchange matter. An open system can interact with its surroundings by exchanging both matter and energy.
Non-equilibrium thermodynamics is a branch of thermodynamics that deals with physical systems that are not in thermodynamic equilibrium but can be described in terms of macroscopic quantities that represent an extrapolation of the variables used to specify the system in thermodynamic equilibrium. Non-equilibrium thermodynamics is concerned with transport processes and with the rates of chemical reactions.
In thermodynamics, a quasi-static process, also known as a quasi-equilibrium process, is a thermodynamic process that happens slowly enough for the system to remain in internal physical thermodynamic equilibrium. An example of this is quasi-static expansion of a mixture of hydrogen and oxygen gas, where the volume of the system changes so slowly that the pressure remains uniform throughout the system at each instant of time during the process. Such an idealized process is a succession of physical equilibrium states, characterized by infinite slowness.
In science, a process that is not reversible is called irreversible. This concept arises frequently in thermodynamics. All complex natural processes are irreversible, although a phase transition at the coexistence temperature is well approximated as reversible.
The laws of thermodynamics are a set of scientific laws which define a group of physical quantities, such as temperature, energy, and entropy, that characterize thermodynamic systems in thermodynamic equilibrium. The laws also use various parameters for thermodynamic processes, such as thermodynamic work and heat, and establish relationships between them. They state empirical facts that form a basis of precluding the possibility of certain phenomena, such as perpetual motion. In addition to their use in thermodynamics, they are important fundamental laws of physics in general and are applicable in other natural sciences.
The Joule expansion is an irreversible process in thermodynamics in which a volume of gas is kept in one side of a thermally isolated container, with the other side of the container being evacuated. The partition between the two parts of the container is then opened, and the gas fills the whole container.
In physical science, an isolated system is either of the following:
- a physical system so far removed from other systems that it does not interact with them.
- a thermodynamic system enclosed by rigid immovable walls through which neither mass nor energy can pass.
In thermodynamics, a thermodynamic state of a system is its condition at a specific time; that is, fully identified by values of a suitable set of parameters known as state variables, state parameters or thermodynamic variables. Once such a set of values of thermodynamic variables has been specified for a system, the values of all thermodynamic properties of the system are uniquely determined. Usually, by default, a thermodynamic state is taken to be one of thermodynamic equilibrium. This means that the state is not merely the condition of the system at a specific time, but that the condition is the same, unchanging, over an indefinitely long duration of time.
Thermodynamic work is one of the principal processes by which a thermodynamic system can interact with its surroundings and exchange energy. This exchange results in externally measurable macroscopic forces on the system's surroundings, which can cause mechanical work, to lift a weight, for example, or cause changes in electromagnetic, or gravitational variables. The surroundings also can perform work on a thermodynamic system, which is measured by an opposite sign convention.
In classical thermodynamics, entropy is a property of a thermodynamic system that expresses the direction or outcome of spontaneous changes in the system. The term was introduced by Rudolf Clausius in the mid-19th century to explain the relationship of the internal energy that is available or unavailable for transformations in form of heat and work. Entropy predicts that certain processes are irreversible or impossible, despite not violating the conservation of energy. The definition of entropy is central to the establishment of the second law of thermodynamics, which states that the entropy of isolated systems cannot decrease with time, as they always tend to arrive at a state of thermodynamic equilibrium, where the entropy is highest. Entropy is therefore also considered to be a measure of disorder in the system.
In thermodynamics, entropy is a numerical quantity that shows that many physical processes can go in only one direction in time. For example, cream and coffee can be mixed together, but cannot be "unmixed"; a piece of wood can be burned, but cannot be "unburned". The word 'entropy' has entered popular usage to refer a lack of order or predictability, or of a gradual decline into disorder. A more physical interpretation of thermodynamic entropy refers to spread of energy or matter, or to extent and diversity of microscopic motion.
In thermodynamics, heat is the thermal energy transferred between systems due to a temperature difference. In colloquial use, heat sometimes refers to thermal energy itself. Thermal energy is the kinetic energy of vibrating and colliding atoms in a substance.
Temperature is a physical quantity that quantitatively expresses the attribute of hotness or coldness. Temperature is measured with a thermometer. It reflects the average kinetic energy of the vibrating and colliding atoms making up a substance.
A thermodynamic operation is an externally imposed manipulation that affects a thermodynamic system. The change can be either in the connection or wall between a thermodynamic system and its surroundings, or in the value of some variable in the surroundings that is in contact with a wall of the system that allows transfer of the extensive quantity belonging that variable. It is assumed in thermodynamics that the operation is conducted in ignorance of any pertinent microscopic information.
